Methods and apparatus for producing alkyl esters from a reaction mixture containing acidified soap stock, alcohol feedstock, and acid

ABSTRACT

Embodiments herein relate to the production of alkyl esters from acidified soap stock. In an embodiment, a process for producing alkyl esters is provided. The process can include mixing acidified soap stock with an alcohol, water, carbon dioxide, and/or carbon monoxide, to form a reaction mixture, and contacting the reaction mixture with a catalyst under supercritical conditions for the alcohol, the catalyst including a metal oxide. Other embodiments are also included herein.

This application claims the benefit of U.S. Provisional Application No. 62/627,518, filed Feb. 7, 2018, the content of which is herein incorporated by reference in its entirety.

FIELD

Embodiments herein relate to the production of alkyl esters from acidified soap stock. More specifically, embodiments herein relate to methods and apparatus for producing alkyl esters from acidified soap stock in a reaction mixture containing an alcohol, carbon dioxide (CO₂), carbon monoxide (CO), and/or one or more acids, and a metal oxide catalyst.

BACKGROUND

Biodiesel is a processed fuel that can be derived from biological sources such as refined plant oils. Biodiesel can be utilized alone or mixed with conventional petroleum-based diesel for use in most standard diesel engines. Biodiesel can also be utilized as a heating fuel in commercial and domestic boilers.

Biodiesel can be considered an environmentally friendly alternative to petroleum-based fossil fuels. For example, use of biodiesel can result in an overall reduction in greenhouse gas emissions and can be produced domestically, resulting in a lower dependence on fossil fuel imports.

Biodiesel can contain one or more long-chain fatty acid alkyl esters, including, but not limited to, fatty acid methyl esters, fatty acid ethyl esters, fatty acid propyl esters and fatty acid isopropyl esters formed from a transesterification or esterification reaction. Fatty acid alkyl esters can be created from the transesterification of triglycerides present in plant oil feedstocks and/or animal fat feedstocks. Fatty acid alkyl esters can also be created from the esterification of free fatty acids present in acidified soap stocks. The conversion to fatty acid alkyl esters can be produced by catalyzed or uncatalyzed reactions.

Soap stocks can be obtained as a byproduct of crude vegetable oil refining performed to remove undesired components from the triglyceride fraction of the oils.

SUMMARY

Embodiments herein relate to the production of alkyl esters from acidified soap stock. More specifically, embodiments herein relate to methods and apparatus for producing alkyl esters from acidified soap stock in a reaction mixture containing an alcohol, CO₂, CO, and/or one or more acids, and a metal oxide catalyst.

In an embodiment, a process for producing alkyl esters is provided. The process can include mixing a soap stock and one or more acids to form an acidified soap stock, and then mixing the acidified soap stock with an alcohol and carbon dioxide to form a reaction mixture. The process can include the step of contacting the reaction mixture with a catalyst under supercritical conditions for the alcohol, where the catalyst can be a metal oxide.

In some embodiments, the metal oxide catalyst can be selected from the group including alumina, titania, zirconia, and hafnia.

In some embodiments, the metal oxide catalyst can include an unmodified metal oxide including alumina, titania, zirconia, and hafnia.

In some embodiments, the metal oxide catalyst can include titania.

In some embodiments, the carbon dioxide can be present in an amount equal to at least 0.1 wt. percent of the mass of the alcohol added.

In some embodiments, the soap stock can include a byproduct derived from tall oil, rapeseed oil, soybean oil, canola oil, cottonseed oil, grape seed oil, mustard seed oil, corn oil, linseed oil, sunflower oil, poppy-seed oil, walnut oil, peanut oil, rice bran oil, camellia oil, castor oil, and olive oil, palm kernel oil, coconut oil, rice oil, algae oil, seaweed oil, or Chinese Tallow tree oil.

In some embodiments, the acidified soap stock can have an acid number of greater than or equal to 3 mg KOH/g oil.

In some embodiments, the process can further include the step of contacting the reaction mixture with a catalyst to drive the conversion of the acidified soap stock from an acid number of equal to 3 mg KOH/g oil to an acid number of less than or equal to 0.5 mg KOH/g oil.

In some embodiments, the process can further include the addition of an organic acid, a Bronsted acid, or an inorganic acid to the reaction mixture.

In some embodiments, the process can further include mixing an inorganic base or and organic base into the reaction mixture.

In some embodiments of the process, the step of contacting the reaction mixture with a catalyst can be performed at a temperature of between 200 and 400 degrees Celsius.

In some embodiments of the process, the step of contacting the reaction mixture with a catalyst can be performed at a pressure of between 1000 and 5000 psi.

In some embodiments of the process, contacting the reaction mixture with a catalyst can be performed with a residence time of less than 60 seconds.

In some embodiments of the process, a catalyst having particles with an average particle size of 0.2 microns to 2 millimeters can be used.

In some embodiments of the process, a catalyst having a porosity of between 0.3 and 0.6 can be used.

In some embodiments of the process, a catalyst having a pore volume of between 0 and 0.6 ml/gram can be used.

In some embodiments of the process, a particulate metal oxide having a surface area of between 1 and 200 m²/gram can be used.

In some embodiments of the process, a C1-C6 alcohol, such as methanol or ethanol, can be used.

In some embodiments, the process can further include the step of removing residual free fatty acids from the reaction mixture.

In some embodiments, the process can further include removing residual free fatty acids from the reaction mixture by adding dimethyl carbonate to the reaction mixture.

In some embodiments, the process can further include removing residual free fatty acids from the reaction mixture by adsorbing the free fatty acids to a metal oxide substrate and separating the reaction mixture from the metal oxide substrate.

In some embodiments, the process can include the production of an amount of alkyl esters that is at least 10% by weight greater than that produced by an otherwise identical reaction mixture lacking the carbon dioxide and/or one or more acids under the same reaction conditions and residence time.

In some embodiments, a process for producing alkyl esters is included. The process can include mixing a soap stock and one or more first acids to form an acidified soap stock, mixing the acidified soap stock with an alcohol and a second acid to form a reaction mixture, the second acid including carbonic acid and/or one or more organic acids, and contacting the reaction mixture with a catalyst under supercritical conditions for the alcohol, the catalyst including a metal oxide selected from the group including alumina, titania, zirconia, and hafnia, wherein the metal oxide has been pretreated with a Bronsted acid or a Bronsted base.

In some embodiments, the process can include the use of a metal oxide that has been pretreated with a Bronsted acid selected from the group consisting of hydrobromic acid, hydrochloric acid, hydroiodic acid, nitric acid, sulfuric acid, perchloric acid, boric acid, chloric acid, phosphoric acid, pyrophosphoric acid, methanethiol, chromic acid, permanganic acid, phytic acid and ethylenediamine tetramethyl phosphonic acid (EDTPA).

In some embodiments, a process for producing alkyl esters via esterification from an acidified soap stock is provided. The process can include mixing a soap stock and one or more first acids to form an acidified soap stock, and mixing the acidified soap stock with an alcohol and a second acid form a reaction mixture. In some cases, the second acid can include carbon dioxide and/or one or more organic acids. The process can also include pumping the reaction mixture into a housing including a porous catalyst such that the reaction mixture comes into contact with the porous catalyst. The porous catalyst can have an average particle size of 0.2 microns to 1 millimeter. The temperature and pressure within the housing can bet set to supercritical conditions for the alcohol. In some embodiments, the porous catalyst can include a metal oxide such as one or more of alumina, titania, zirconia, and hafnia. The process can further include collecting a reaction product from the housing, where the reaction product can include esters in an amount at least equal to 80% of the free fatty acid or carboxylic acid in the soap stock on a molar basis.

In an embodiment, a process for producing alkyl esters is provided. The process can include mixing a soap stock and one or more acids to form an acidified soap stock, and mixing the acidified soap stock with an alcohol and carbon monoxide to form a reaction mixture. The reaction mixture can be contacted with a catalyst under supercritical conditions for the alcohol, where the catalyst can include a metal oxide.

In some embodiments of the process, carbon monoxide can be present in an amount equal to at least 0.1 wt. percent of the mass of the alcohol added.

This summary is an overview of some of the teachings of the present application and is not intended to be an exclusive or exhaustive treatment of the present subject matter. Further details are found in the detailed description and appended claims. Other aspects will be apparent to persons skilled in the art upon reading and understanding the following detailed description and viewing the drawings that form a part thereof, each of which is not to be taken in a limiting sense. The scope herein is defined by the appended claims and their legal equivalents.

BRIEF DESCRIPTION OF THE FIGURES

Aspects may be more completely understood in connection with the following drawings, in which:

FIG. 1 is a schematic view of an exemplary process in accordance with the embodiments herein.

FIG. 2 is a schematic view of an exemplary process in accordance with the embodiments herein.

FIG. 3 is a schematic diagram of a production apparatus in accordance with the embodiments herein.

While embodiments are susceptible to various modifications and alternative forms, specifics thereof have been shown by way of example and drawings, and will be described in detail. It should be understood, however, that the scope herein is not limited to the particular embodiments described. On the contrary, the intention is to cover modifications, equivalents, and alternatives falling within the spirit and scope herein.

DETAILED DESCRIPTION

As discussed above, biodiesel formed from one or more long-chain fatty acid alkyl esters, can be created by the esterification of acidified soap stock feedstocks. The esterification reactions can be catalyzed under homogeneous or heterogeneous reaction conditions.

Without wishing to be bound by any particular theory, it is believed that the addition of carbon dioxide (CO₂) and/or carbon monoxide (CO) to the reaction mixtures described herein can further catalyze the esterification of free fatty acids found in acidulated soap stocks into biodiesel fuels. It is also believed that addition of CO₂ and/or CO can further drive the esterification reactions to completion. In some cases, the acid number can be less than 0.5 (mg KOH/g oil) and specifically as close to 0 (mg KOH/g oil) as possible.

Referring now to FIG. 1, a schematic view of an exemplary process 100 for producing alkyl esters is shown. The process can begin with mixing together an acidified soap stock 102, an alcohol feed stock 104, and at least one of CO₂ 106, CO 107, and/or one or one or more acids 108 to form a reaction mixture at 110. It will be appreciated that in some cases the process can begin with mixing together an acidified soap stock 102, an alcohol feed stock 104, and CO₂ 106. In some embodiments, the process can begin with mixing together an acidified soap stock 102, an alcohol feed stock 104, and one or more acids 108. In yet other embodiments, the process can begin with mixing together an acidified soap stock 102, and alcohol feed stock 104, CO₂ 106, and one or more acids 108. In some embodiments, the process can begin with mixing together an acidified soap stock 102, an alcohol feed stock 104, and CO 107. In yet other embodiments, the process can begin with mixing together an acidified soap stock 102, and alcohol feed stock 104, CO 107, and one or more acids 108.

It will be appreciated that in some embodiments the reaction mixture can contain an amount of water suitable to react with CO₂ gas to form carbonic acid. Without wishing to be bound by any particular theory, it is believed that CO₂ gas dissolves in water to form carbonic acid (H₂CO₃) as follows:

CO₂+H₂O↔H₂CO₃

The amount of water suitable for use herein can include the addition of greater than or equal to 0.05% by weight (by wt.) water added to the reaction mixture. In some embodiments, the amount of water added to the reaction mixture can include 0.05% by wt., 0.1% by wt., 0.5% by wt., 1.0% by wt., 1.5% by wt., 2% by wt., 3% by wt., 4% by wt., 5% by wt., or 10% by wt. It will be appreciated that amount of water added to the reaction mixture can fall within a range, wherein any of the forgoing weight percentages can serve as the lower or upper bound of the range, provided that the lower bound of the range is a value less than the upper bound of the range. It will be appreciated that in some embodiments, gaseous CO₂ can first be passed through water to form carbonic acid and then mixed into the reaction mixture. In other cases, the CO₂ can be added to the reaction mixture once it reaches the reactor 334, as will be discussed further below in reference to FIG. 3. In some embodiments, the water can be introduced into the reaction mixture as a component of the alcohols used herein.

It will be appreciated that in some embodiments the reaction mixture can contain an amount of water vapor suitable for reaction with CO to form CO₂ at the high temperatures and pressures used in the reactions herein. In some cases, CO can be added directly to the reaction mixture. In other cases, the CO can be added to the reaction mixture once it reaches the reactor 334, as will be discussed further below in reference to FIG. 3. Without wishing to be bound by any particular theory, it is believed that CO can react with water vapor at high temperatures to form carbon dioxide and hydrogen gases.

The acidified soap stock 102 can be derived from various plant oil sources as described more fully below. The alcohol feed stock 104 can include one or more types of alcohol as described more fully below. The one or more acids 108 can include one or more types of acids as described more fully below. In some embodiments, one or more acidified soap stocks, one or more alcohol feed stocks, and CO₂ and/or CO are mixed together to form a reaction mixture. In other embodiments, one or more acidified soap stocks, one or more alcohol feed stocks, and one or more acids are mixed together to form a reaction mixture. In yet other embodiments, one or more acidified soap stocks, one or more alcohol feed stocks, CO₂, CO, and/or one or more acids are mixed together to form a reaction mixture.

Mixing the separate components to form a reaction mixture can be done in a separate mixing vessel relative to the vessel containing the separate components, or it can be done by simply injecting one component at a time into the other components until all components are combined. In some embodiments, the amount of alcohol supplied can be in a molar excess to the stoichiometric ratio of the reaction. By way of example, for the esterification of a free fatty acid, the stoichiometric ratio is 1 moles of alcohol for every 1 mole of free fatty acid. However, the reaction can be pushed farther towards completion by adding a molar excess of alcohol. In some embodiments, a molar excess of alcohol can also be supplied to allow for the transesterification of any triglycerides, monoglycerides, or diglycerides that may present in the acidified soap stock.

Accordingly, in an embodiment, an amount of alcohol can be added to the reaction mixture that exceeds the ratio of 1 parts alcohol to 1 part free fatty acid. For example, in some embodiments, the amount of alcohol added to the reaction mixture can be 2 parts alcohol to 1 part free fatty acid. In some embodiments, the amount of alcohol added to the reaction mixture can be 4 parts alcohol to 1 part free fatty acid. In some embodiments, the amount of alcohol added to the reaction mixture can be 6 parts alcohol to 1 part free fatty acid. However, in other embodiments the alcohol can be added to the reaction mixture in a less than or equal to the stoichiometric ratio. For example, in some embodiments, the reaction mixture can have a ratio of 0.5-1 moles of alcohol to 1 mole of free fatty acid.

Similarly, the reaction can be pushed even farther towards completion by adding CO₂ and/or one or more acids to catalyze the esterification of free fatty acids in the reaction mixture. Without wishing to be bound by theory, it is believed that the addition of CO₂ to the reaction mixture can result in the formation of carbonic acid (H₂CO₃) due to the reaction between CO₂ and water present in the reaction mixture. Carbonic acid and/or one or more additional acids can catalyze the esterification of free fatty acids or otherwise enhance the conversion of free fatty acids to esters.

In some embodiments, the process can include mixing CO₂ into the reaction mixture in an amount equal to at least 0.1 weight percent (wt. percent or wt. %) of the mass of the alcohol added. In some embodiments, the process can include adding CO₂ in an amount equal to at least 1.0 wt. percent of the mass of the alcohol added. In some embodiments, the process can include adding CO₂ in an amount equal to at least 0.1 wt. %, 1.0 wt. %, 2 wt. %, 3 wt. %, 4 wt. %, 5 wt. %, 6 wt. %, 7 wt. %, 8 wt. %, 9 wt. %, 10 wt. %, 15 wt. %, 20 wt. %, 25 wt. %, 30 wt. %, 40 wt. %, or 50 wt. % of the mass of the alcohol added. In some embodiments, an amount of CO₂ can be added to achieve maximum CO₂ solubility in water at the temperatures and pressures suitable for use in the reactions described herein. In some embodiments, the reaction mixture can contain carbonic acid at a concentration of at least 0.05, 0.1, 0.25, 0.5, 0.75, 1, 1.5, 2, 3, 4, 5, 7.5, 10, 15 or 20 M, or can have a concentration falling within a range between any of the foregoing.

The pH of the reaction mixture can vary. In some embodiments, the pH can be about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 13.5, or the pH can fall within a range between any of the foregoing. In some embodiments, the pH of the reaction mixture can be acidic. In some embodiments, the pH of the reaction mixture can be less than 7. In some embodiments, the pH of the reaction mixture can be less than 3. In some embodiments, the pH of the reaction mixture can be from about 2 to about 4.

In some embodiments, the process can include mixing CO into the reaction mixture in an amount equal to at least 0.1 weight percent (wt. percent or wt. %) of the mass of the alcohol added. In some embodiments, the process can include adding CO in an amount equal to at least 1.0 wt. percent of the mass of the alcohol added. In some embodiments, the process can include adding CO in an amount equal to at least 0.1 wt. %, 0.5 wt. %, 1.0 wt. %, 2 wt. %, 3 wt. %, 4 wt. %, 5 wt. %, 6 wt. %, 7 wt. %, 8 wt. %, 9 wt. %, 10 wt. %, 15 wt. %, 20 wt. %, 25 wt. %, 30 wt. %, 40 wt. %, or 50 wt. % of the mass of the alcohol added. In some embodiments, an amount of CO can be added to achieve maximum CO solubility in water at the temperatures and pressures suitable for use in the reactions described herein.

In some embodiments, the process can include mixing one or more acids into the reaction mixture in an amount equal to at least 0.1 weight percent (wt. percent or wt. %) of the mass of the alcohol added. In some embodiments, the process can include adding one or more acids present in an amount equal to at least 1.0 wt. percent of the mass of the alcohol added. In some embodiments, the process can include adding one or more acids present in an amount equal to at least 0.1 wt. %, 1.0 wt. %, 2 wt. %, 3 wt. %, 4 wt. %, 5 wt. %, 6 wt. %, 7 wt. %, 8 wt. %, 9 wt. %, 10 wt. %, 15 wt. %, 20 wt. %, 25 wt. %, 30 wt. %, 40 wt. %, or 50 wt. % of the mass of the alcohol added.

In some embodiments, the amount of alkyl esters produced by adding CO₂, CO, or one or more acids can be at least 10% by weight greater than that produced by an otherwise identical reaction mixture lacking the CO₂, CO, and one or more acids under the same reaction conditions and residence time.

In some embodiments, the reaction mixture can include one or more organic bases or inorganic bases to further catalyze the transesterification of triglycerides to completion. In some embodiments, the reaction mixture can include a Lewis base. Some examples for suitable Lewis bases can include anions formed from the dissociation of acids such as hydrobromic acid, hydrochloric acid, hydroiodic acid, nitric acid, sulfuric acid, perchloric acid, boric acid, chloric acid, phosphoric acid, pyrophosphoric acid, chromic acid, permanganic acid, phytic acid and ethylenediamine tetramethyl phosphonic acid (EDTPA), and the like. Other Lewis bases can include, but not be limited hydroxide ion as formed from the dissociation of bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. Suitable inorganic bases can include, but not be limited to lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide, and the like.

In some embodiments, the reaction mixture can also include a carrier compound. A carrier compound can serve various purposes including helping to reduce the viscosity of the reaction mixture. The carrier compound can be a compound that is non-reactive under the reaction conditions. Examples of carrier compounds can include, but are not limited to, hexane, saturated cycloalkanes, and fluorinated hydrocarbons. Carrier compounds can be present in the reaction mixture in an amount from 0.0 wt. % to 99.9 wt. %. Conversely, active components, such as an acidified soap stock and the alcohol feed stock can be present in the reaction mixture in an amount from 0.1 wt. % to 100.0 wt. %.

After mixing all components together to form a reaction mixture, the reaction mixture can be contacted with a catalyst at 112. In some embodiments, the catalyst can be a metal oxide catalyst. Suitable metal oxide catalysts for use herein are described more fully below. In some embodiments, step of contacting the reaction mixture with a metal catalyst can include contacting the reaction mixture with a catalyst under supercritical conditions for the alcohol. In some embodiments, step of contacting the reaction mixture with a metal catalyst can include contacting the reaction mixture with a catalyst under supercritical conditions for CO₂.

In some embodiments, the metal oxide catalyst can have an acid or base adsorbed thereto. In some embodiments, the metal oxide can be unmodified and does not have an acid or base adsorbed thereto. In some embodiments, the metal oxide catalyst can be disposed within a reactor having a housing. By way of example, the metal oxide catalyst can be disposed within a column. The metal oxide catalyst can be packed within the housing such that the reaction mixture must pass between particles of the metal oxide catalyst as it passes through the housing. The housing can be constructed to withstand the high pressures and temperatures associated with supercritical conditions of water, alcohols, and CO₂, and CO. Supercritical conditions suitable for use herein are discussed further below.

After the reaction mixture is passed over the metal oxide catalyst and the reaction is driven to a desired degree of completion, the reaction products in the effluent from the reaction can be separated from one another at 114. In some embodiments, the main fraction is an alkyl ester fraction, which can be stored in a storage tank or it can be immediately utilized as biodiesel in a diesel engine. Additional byproducts of the reaction can be further separated from the rest of the reaction products. By way of example, in some embodiments, the reaction produces glycerol as a byproduct. It will be appreciated that as used herein the terms “glycerol”, “glycerine” and “glycerin” are all equivalent. The glycerol can be readily separated from the alkyl esters, since glycerol has a tendency to phase separate from alkyl esters making the separation process relatively straightforward. Various types of separation devices can be used, such as a centrifugal fluid separator or the like. Additional reaction products can include aldehydes and ethers, such as dimethyl ether. The glycerol and other reaction products can be stored and later sold, used as a feed stock for other chemical processes, used as a feedstuff for animals, or used for human foods after further purification.

In some embodiments, the method may optionally include a step of removing free fatty acids from the reaction mixture, if present, at 116. This step of removing free fatty acids can also be referred to as a “polishing” step. This can be performed at various points in the production process such as before or after the step of separating reaction product at 114 and/or before or after passing the reaction mixture over the catalyst at 112.

In some embodiments, removing residual free fatty acids from the reaction mixture can include adding a compound to the reaction mixture that serves to react with the residual free fatty acids. Such as compound can be referred to as a residual free fatty acid scavenger or scavenging compound. An exemplary scavenging compound for this purpose is dimethyl carbonate. However, other compounds can also be used as a scavenging compound. In some embodiments, the scavenging compound can be added to the reaction mixture before contacting the reaction mixture with the catalyst. In other embodiments, the scavenging compound can be added after the transesterification reaction has taken place.

In some other embodiments, the residual free fatty acids in the reaction mixture can be removed in other ways. For example, a material can be used to absorb residual free fatty acids compounds. Specifically, metal oxide media containing acid/base surface properties such as Lewis acid sites, Bronsted base sites, and/or Bronsted acid sites can be used to selectively bind, at relatively low temperatures, and remove organic acids from fatty acid alkyl ester reaction products. This can be performed in various ways. In an embodiment, an appropriate metal oxide media can be disposed within the interior volume of a housing. A crude reaction product mixture containing free fatty acids can then be pumped into the housing. After contacting the metal oxide media, free fatty acids in the crude reaction product mixture can be bound to the metal oxide media. Next, the purified reaction product mixture can be separated out, leaving behind the metal oxide media and bound organic acids.

In some embodiments, the reaction can be performed under conditions sufficient to result in the production of aldehydes and/or ethers as a decomposition byproduct of glycerol instead of glycerol itself. In some embodiments, the reaction products include gases, such as dimethyl ether. While not intending to be bound by theory, the production of gases as a byproduct can be advantageous because it is believed to be easier to separate various gases from fatty acid alkyl esters than it is to separate out glycerol from fatty acid alkyl esters.

Depending on the specific metal oxide used to catalyze the reaction of free fatty acids to form alkyl esters, a need may arise to periodically reprocess the catalyst. For example, in the context of modified metal oxide catalysts, the catalyst can be periodically retreated with an acid (such as sulfuric acid or phosphoric acid) or a base (such as sodium hydroxide). In the context of a continuous flow production facility, stopping production to reprocess the catalyst or to replace the catalyst may be costly and inefficient. As such, in some embodiments, at least two different reactors can be included such that feed stock flow can be diverted back and forth between the reactors so that one can be taken “off-line” and recharged without interrupting the production process. After the particular reactor is recharged, such as through treatment with an acid or a base, it can be returned to service.

Because the reaction mixture is passed over a metal oxide catalyst at an elevated temperature, there is a need to dissipate heat after the reaction has gone to completion. In an embodiment, heat from the effluent products is used to heat up the acidified soap stock, alcohol feed stock, CO₂, CO, and/or acid through a counter-flow heat exchanger. Transferring heat from the effluent flow to the feed stock flow can make the alkyl ester production process more energy efficient since less energy is used to get the reaction mixture up to the desired temperature and promotes the mixing of the reactants for faster conversion within the continuous reactor. In some embodiments the reactor housing can be a ceramic that can withstand elevated temperatures and pressures. In some embodiments, the housing reactor housing can be a metal or an alloy of metals such as INCONEL.

In some embodiments, the reaction mixture reaches the desired level of reaction completion after one pass over the metal oxide catalyst bed or packing. However, in some embodiments, the effluent flow may be rerouted over the same metal oxide catalyst or routed over another metal oxide catalyst bed or packing so that reaction is pushed farther toward completion in measured stages.

In some embodiments two or more reactors having metal oxide catalyst beds disposed therein can be used to convert one or more acidified soap stocks to alkyl esters. For example, in some embodiments, a reaction mixture can be passed through both an acid-modified metal oxide catalyst bed and a base-modified metal oxide catalyst bed in succession. The reaction temperatures within each catalyst bed can be either the same or different. In a particular embodiment, a reaction mixture is first passed through an acid-modified metal oxide catalyst bed at a relatively lower temperature and then passed through a base-modified metal oxide catalyst bed at a relatively higher temperature. The acid-modified catalyst reaction step can serve to reduce the amount of free fatty acids in the reaction mixture before it is passed on to the base-modified catalyst reaction step.

In some embodiments, an acid-modified metal oxide catalyst (such as sulfuric or phosphoric acid modified) and a base-modified metal oxide catalyst (such as sodium hydroxide modified) can be separately formed but then disposed together within a housing. In such an approach, the reaction mixture passing through the housing can be simultaneously exposed to both the acid and base modified metal oxide catalysts.

In some embodiments, two different metal oxides (such zirconia and titania) can be separately formed but then disposed together within a reactor housing. In such an approach, the reaction mixture passing through the housing can be simultaneously exposed to both metal oxide catalysts.

It will be appreciated that the process 100 shown in FIG. 1 can be conducted in a continuous flow mode. By way of example, the process 100 can be carried out such that all of the steps are taking place simultaneously and the feedstocks, CO₂, CO, and/or one or more acids are continuously being resupplied and turned into biodiesel fuel. While not intending to be bound by theory, continuous flow production of biodiesel fuel can offer substantial advantages over batch production, including being more economical. However, in another embodiment, the flow may be periodically stopped to allow for the reaction to proceed to completion and then turned back on to continue the production cycle. This process of stopping and restarting flow can be referred to as a semi-continuous flow mode.

Referring now to FIG. 2, a schematic view is shown of a method 200 of producing alkyl esters in accordance with the embodiments herein. Reactant materials (such one or more acidified soap stocks, one or more alcohol feed stocks, CO₂, CO, and/or one or more acids) can be stored in tanks before being used at 202. In some embodiments each reactant can be stored in individual tanks. In other embodiments, the reactants can be mixed within the same tank. The tanks can be heated or unheated. The reactant materials can be pumped at a high pressure at 204. The high pressure can be sufficient to prevent vaporization of the feed stock materials and acids at the temperature of the reaction. Next, the feed stock materials and acids can be reacted in order to produce a reaction product composition that can include alkyl esters (such as biodiesel fuel) and byproducts (including aldehydes, ethers, and glycerol) at 206. After the reaction goes to completion, any volatile materials (such as left over alcohol or other organic compounds) and byproduct gases (such as ethers) are removed from the reaction product composition at 208. Any remaining byproducts (such as glycerol) can be separated from the alkyl esters (such as biodiesel fuel) at 210. Finally, end products such as alkyl esters and byproducts such as glycerol can be stored until being used in other processes or until being shipped away from the production plant at 212.

Referring now to FIG. 3, a schematic diagram is shown of an alkyl ester production apparatus 300 for producing alkyl esters in accordance with the embodiments herein. An acidified soap stock can be held in acidified soap stock tank 302. In some embodiments, the acidified soap stock tank 302 can be heated. In some embodiments, the acidified soap stock tank 302 can maintain the acidified soap stock at a temperature high enough to keep the acidified soap stock in a liquid state prior to forming a reaction mixture with other reactants. Upon exit from acidified soap stock tank 302, the acidified soap stock can pass through a soap stock pump 310 before passing through a heat exchanger 318 where it can absorb heat from downstream products.

An alcohol feed stock can be held in an alcohol tank 304. In some embodiments, the alcohol tank 304 can be heated. Upon exit from the alcohol tank 304, the alcohol feed stock can pass through an alcohol pump 312 before passing through a heat exchanger 318 where it can absorb heat from downstream products or from a pre-heater (not shown). The CO₂ can be held in a pressurized tank 306 and the CO can be held in a pressurized tank 307. The CO₂ can pass through a back pressure regulator 314 before passing through a heat exchanger 318 where it can absorb heat from downstream products from a pre-heater (not shown). The CO can pass through a back pressure regulator 315 before passing through a heat exchanger 318 where it can absorb heat from downstream products from a pre-heater (not shown).

One or more acids can be held in acid tank 308. In some embodiments, the acid tank 308 can be heated. The acid can pass through an acid pump 316 before passing through a heat exchanger 318 where it can absorb heat from downstream products from a pre-heater (not shown). In some embodiments, the heat exchanger 318 is a counter-flow heat exchanger.

An exemplary counter-flow heat exchanger is described in U.S. Pat. No. 6,666,074, the contents of which are herein incorporated by reference. For example, a pipe or tube containing the effluent flow can be routed past a pipe or tube holding the feed stock flow or the reaction mixture. In some embodiments, a pipe-in-pipe counter-flow heat exchanger can be used. In some embodiments, a thermally conductive material, such as a metal, connects the effluent flow with the feed stock flow so that heat can be efficiently transferred from the effluent products to the feed stocks or the reaction mixture.

While FIG. 3 shows CO₂ added as a separate reactant in parallel with other reactant materials, it will be appreciated that CO₂ can alternatively be mixed directly into one or more reaction tanks, including acidified soap stock tank 302, alcohol tank 304, or acid tank 308. For example, in some embodiments, the CO₂ can be added directly to the alcohol tank 304. In other embodiments, the CO₂ can be added directly to a reaction mixture in the reactor 334. Similarly, while FIG. 3 shows CO added as a separate reactant in parallel with other reactant materials, it will be appreciated that CO can alternatively be mixed directly into one or more reaction tanks, including acidified soap stock tank 302, alcohol tank 304, or acid tank 308. For example, in some embodiments, the CO can be added directly to alcohol tank 304. In other embodiments, the CO can be added directly to a reaction mixture in the reactor 334.

It will be appreciated that the feed stock tanks described herein can optionally include an agitation mechanism and temperature control mechanism to keep the components in the tanks thoroughly mixed and at a relatively constant temperature. In some embodiments, one or all of the acidified soap stock, alcohol, or acid feed stock tanks may include a gas sparger/bubbler so as to displace dissolved oxygen to avoid any oxidation reactions that can potentially occur at high temperatures. In some embodiments, the tank(s) can be continuously sparged with an inert gas, such as nitrogen, to remove dissolved oxygen from the feed stocks. In some embodiments, sparging the tank(s) with nitrogen gas can further limit potential oxidation reactions. Although the acidified soap stock, the alcohol feed stock, the CO₂, and/or the acid feed stock in the embodiment shown in FIG. 3 are in different tanks, it will be appreciated that in some embodiments they can be disposed in the same tank.

In some embodiments the feed stocks, such as the acidified soap stock, can be processed in order to remove particulate matter and other debris before being processed through the reactor 334. By way of example, the feed stocks can be filtered or distilled. In some embodiments the feed stocks can be processed with a continuous centrifuge that can spin out all particulates and in some cases even water from the acidified soap stock.

After passing through the heat exchanger 318, the acidified soap stock passes through a shutoff valve 320 and a filter 322 to remove particulate material of a certain size from the feed stock. Similarly, the alcohol feed stock passes through a shutoff valve 324 and a filter 326, and the acid feed stock passes through shutoff valve 328 and filter 330. The acidified soap stock, alcohol feed stock, CO₂, and/or acid feed stock then pass through a preheater 332 where they are mixed together to form a reaction mixture. The preheater 332 can elevate the temperature of the reaction mixture to a desired level. Many different types of heaters are known in the art and can be used.

It will be appreciated that while acidified soap stock, alcohol feed stock, CO₂, CO, and/or acid feed stock are shown in FIG. 3 as passing through separate shutoff valves and filters, they can also mix within the heat exchanger 318 and exit such that the reaction mixture containing acidified soap stock, alcohol feed stock, and CO₂, CO, and/or acid feed stock can pass through a single shutoff valve and filter sequence (not shown).

In some embodiments, a pre-heating step can be performed to raise the temperature of the reactants before they enter a reactor housing containing the metal oxide catalyst. Preheating of the reactants can be performed in various ways including using a heating block, a heating bath, a counter-current heat exchanger, etc. While not intending to be bound by theory, it is believed that pre-heating the reactants can improve the efficiency of the reaction in part because of the effect pre-heating has on the maintenance of temperatures within the reactor housing. In some embodiments, the reactants can be preheated to at least about 70% of the reaction temperature inside of the reactor housing containing the metal oxide catalyst. In some embodiments, the reactants can be preheated to at least about 80% of the reaction temperature inside of the reactor housing containing the metal oxide catalyst. In some embodiments, the reactants can be preheated to at least about 90% of the reaction temperature inside of the reactor housing containing the metal oxide catalyst. In some embodiments, reactants can be preheated to at least about 95% of the reaction temperature inside of the reactor housing containing the metal oxide catalyst. In some embodiments, reactants can be preheated to substantially the same temperature as the reaction temperature inside of the reactor housing containing the metal oxide catalyst. In some embodiments, reactants can be preheated to a temperature higher than the reaction temperature inside of the reactor housing containing the metal oxide catalyst. In some cases, the reactants are raised to supercritical conditions for temperature and pressure for the alcohol feed stock before entering the inside of the reactor housing. In some cases, the reactants are raised to supercritical conditions for temperature and pressure for the CO₂ or one or more acids before entering the inside of the reactor housing.

After preheating, the reaction mixture can then pass through a reactor 334 where the reaction mixture is converted into alkyl esters forming a reaction product mixture. The reactor 334 can include a metal oxide catalyst. For example, the reactor can include an acid (such as sulfuric acid or phosphoric acid) modified or base (such as sodium hydroxide) modified metal oxide catalyst, or an unmodified metal oxide catalyst. The reaction product mixture can pass through a backpressure regulator 336 and the heat exchanger 318 before passing on to a distillation apparatus 338. The distillation apparatus 338 can be configured to carry out fractional distillation in order to remove excess alcohol from the reaction product mixture and/or isolate one or more fractions of the biodiesel fuel that meets ASTM specifications. The distillation apparatus 338 can include any desired number of theoretical plates in order to recover a desired amount of the excess alcohol and to remove any other byproducts of the reaction. In some embodiments, the recovered alcohol can be de-watered by using molecular sieves. In some embodiments, the alcohol recovered from distillation can be put back into the alcohol tank 304 for reuse.

In many embodiments, the reaction mixture is maintained at an elevated temperature within the reactor. The reactor can be configured to withstand the temperature and pressure under which the reaction mixture is kept. In some embodiments, a heating element is in thermal communication with the reactor so as to be able to heat the reaction mixture up to the desired temperature. If the temperature of the reaction mixture is not sufficiently high, the reaction may proceed more slowly than desired. In some embodiments, the temperature of the reaction mixture is maintained at a temperature of between 200° and 400° Celsius. In some embodiments, the temperature of the reaction mixture is maintained at a temperature of between 100° and 600° Celsius. In some embodiments, the temperature of the reaction mixture is maintained at a temperature of between 350° and 400° Celsius.

In some embodiments, the temperature of the reaction mixture is about 50°, 75°, 100°, 125°, 150°, 175°, 200°, 225°, 250°, 275°, 300°, 325°, 350°, 375°, 400°, 425°, 450°, 475°, 500°, 525°, 550°, 575°, 600°, 625°, 650°, 675° Celsius or hotter. It will be appreciated that temperature of the reaction mixture can fall within a range, wherein any of the forgoing temperatures can serve as the lower or upper bound of the range, provided that the lower bound of the range is a value less than the upper bound of the range. In some embodiments, the temperature of the reaction mixture can be greater than the critical temperature of the alcohol feed stock. In some embodiments, the temperature of the reaction mixture can be greater than the critical temperature of the CO₂ or one or more acids.

Supercritical conditions for water can include a temperature (T) of ≥350° Celsius and pressure (P) of ≥3200 psi. Supercritical conditions for the alcohols described herein can include supercritical conditions for methanol (T≥240° Celsius and P≥1150 psi) and supercritical conditions for ethanol (T≥240° Celsius and P≥890 psi). Supercritical conditions for CO² can include a T≥30° Celsius and P≥105 psi. Supercritical conditions for CO can include a T≥−140° Celsius and P≥507 psi.

However, in some embodiments, the temperature of the reaction mixture can be less than about 500° Celsius. In some embodiments, the temperature of the reaction mixture can be less than about 400° Celsius.

In some embodiments, the reaction mixture is kept under pressure. The reactor can be configured to withstand the pressure under which the reaction mixture is kept. A desirable pressure for the reaction mixture can be estimated with the aid of the Clausius-Clapeyron equation. Specifically, the Clausius-Clapeyron equation can be used to estimate the vapor pressures of a liquid. The Clausius-Clapeyron equation is as follows:

${\ln \left( \frac{P_{1}}{P_{2}} \right)} = {\frac{\Delta \; H_{vap}}{R}\left( {\frac{1}{T_{2}} - \frac{1}{T_{1}}} \right)}$

wherein ΔH_(vap)=is the enthalpy of vaporization; P₁ is the vapor pressure of a liquid at temperature T₁; P₂ is the vapor pressure of a liquid at temperature T₂, and R is the ideal gas law constant.

In some embodiments, the pressure inside the reactor can be greater than the vapor pressures of any of the components of the reaction mixture. In some embodiments, the pressure inside the reactor can be greater than about 500 psi, 600 psi, 700 psi, 800 psi, 900 psi, 1000 psi, 1250 psi, 1500 psi, 1750 psi, 2000 psi, 2250 psi, 2500 psi, 2750 psi, 3000 psi, 3250 psi, 3500 psi, 3750 psi, 4000 psi, 4250 psi, 4500 psi, 4750 psi, 5000 psi, 5250 psi, 5500 psi, 5750 psi, 6000 psi, 6250 psi, 6500 psi, 6750 psi, 7000 psi or higher.

In some embodiments, the pressure is between about 1000 psi and about 5000 psi. In some embodiments, the pressure is between about 1500 psi and about 3500 psi. In some embodiments, the pressure is between about 500 psi and about 2000 psi. In some embodiments, the pressure inside the reactor is greater than the critical pressure of the alcohol used in the reaction. In some embodiments, the pressure inside the reactor is greater than the critical pressure of CO₂ or one or more acids used in the reaction.

The reaction mixture may be passed over the metal oxide catalyst within the reactor for a length of time sufficient for the reaction to reach a desired level of completion. This will in turn depend on various factors including the temperature of the reaction, the chemical nature of the catalyst, the surface area of the catalyst, and the like. The term “residence time” can be used to describe the amount of time in which the reaction product mixture interacts with the catalyst in the reactor. Embodiments herein can include methods and systems wherein the residence time is relatively small while still achieving high percentages of conversion. By way of example, in some embodiments the residence time is less than about 60 seconds. In some embodiment, the residence time is less than about 30 seconds. In some embodiment, the residence time is less than about 10 seconds.

The remaining reaction products can then pass on to a stirred tank 340 where, in some embodiments, the remaining reaction products are mixed with a base solution, such as a sodium hydroxide solution, from a base solution tank 342. The base solution can react with remaining free fatty acids in order to convert them (saponification) into a soap composition. However, it will be appreciated that in other embodiments the residual free fatty acids are removed using other methods such as those described with respect to FIG. 1 above.

The remaining reaction products and the soap composition can then pass on to a separation apparatus 344 that is configured to separate byproducts such as glycerol and the soap composition from the alkyl esters (such as biodiesel). The alkyl esters can be passed into an alkyl ester storage tank 346. The soap composition and the glycerol are can be passed into a byproduct tank 348.

In some embodiments (not shown), a metal oxide can be used as a scrubber to reduce or eliminate certain components from a reaction mixture or feed stock. By way of example, in some embodiments, unmodified zirconia, titania, and/or hafnia can be used to remove free fatty acids from compositions before or after the reaction that produces fatty acid methyl esters. As discussed above, it is believed that free fatty acids can be adsorbed to such metal oxides and therefore removed from the reaction mixture or reaction products.

One advantage of biodiesel fuel is that it can be used to operate existing diesel engines. The proper performance of diesel engines depends on a degree of consistency in the diesel fuel itself. However, various factors can affect the consistency of the fuel made by transesterification including the specific feed stocks used, the particular separation steps used, and the type of catalysis used. For these reasons, the American Society for Testing and Materials (ASTM) has created a standard for biodiesel fuel (ASTM D6751-06a). Embodiments herein can be used to produce a mixture of alkyl esters that meets the specifications of ASTM D6751-06a. Specifically, embodiments herein can include alkyl ester solutions complying with ASTM D6751-06a.

Embodiments can also include a diesel fuel composition including fatty acid alkyl esters as the reaction product of fatty acids from an acidified soap stock, an alcohol feedstock, CO₂, CO, and/or an acid, wherein at least about 50%, 60%, 70%, 75%, 80%, 85%, 90%, 95%, 97%, 98%, or 99% of the free fatty acids on a molar basis are converted into fatty acid methyl esters.

Soap Stocks

Soap stocks suitable for use as feed stocks herein can be obtained as a byproduct of crude vegetable oil refining performed to remove undesired components from the triglyceride fraction of the oils. Soap stocks can include, but not be limited to water, free fatty acids, sodium or potassium soaps of fatty acids, phospholipids, waxes, aldehydes, ketones, mono glycerides, diglycerides, and triglycerides and other fatty compounds. In some embodiments, soap stocks can be rich in free fatty acids and can be a valuable source for biodiesel applications.

Feed stocks suitable for use herein can include soap stock and acidulated soap stock. Acidulation of soap stock to recover the acid oils therein can include adding a strong mineral acid, such as sulfuric acid, to raw a soap stock and allowing the free fatty acids to be released into solution. In some embodiments, the acid used for acidulation of one or more soap stocks can include other strong acids such as nitric acid, hydrochloric acid, phosphoric acid, perchloric acid, hydrobromic acid, hydroiodic acid, etc. In some embodiments, the acidulation can be performed at a relatively low pH at or near pH 2 to pH. In some embodiments, the pH can be close to pH 4.

Soap stocks suitable for use with the embodiments herein can be derived from many different plant sources. In some embodiments, soap stocks can include lipids (e.g., fats or oils) produced from processing any type of land-dwelling or water-dwelling plant. In an embodiment, the soap stocks used can include triglycerides. Many different biological soap stocks derived from plants can be used. By way of example, plant-based soap stocks can include rapeseed oil, soybean oil (including degummed soybean oil), canola oil, cottonseed oil, grape seed oil, mustard seed oil, corn oil, linseed oil, safflower oil, sunflower oil, poppy-seed oil, pecan oil, walnut oil, oat oil, peanut oil, rice bran oil, camellia oil, castor oil, and olive oil, palm oil, coconut oil, rice oil, algae oil, seaweed oil, Chinese Tallow tree oil. Other plant-based biological soap stocks can be obtained from argan, avocado, babassu palm, balanites, borneo tallow nut, brazil nut, calendula, camelina, caryocar, cashew nut, chinese vegetable tallow, cocoa, coffee, cohune palm, coriander, cucurbitaceae, euphorbia, hemp, illipe, jatropha, jojoba, kenaf, kusum, macadamia nuts, mango seed, noog abyssinia, nutmeg, opium poppy, perilla, pili nut, pumpkin seed, rice bran, sacha inche, seje, sesame, shea nut, teased, allanblackia, almond, chaulmoogra, cuphea, jatropa curgas, karanj a seed, neem, papaya, tonka bean, tung, and ucuuba, cajuput, clausena anisata, davana, galbanum natural oleoresin, german chamomile, hexastylis, high-geraniol monarda, juniapa-hinojo sabalero, lupine, melissa officinalis, milfoil, ninde, patchouli, tarragon, and wormwood.

Acidified soap stocks (also referred to herein as acidulated soap stocks) suitable for use with embodiments herein can specifically include low value soap stocks. Low value soap stocks, generally have a relatively high concentration of free fatty acids. One method of assessing the concentration of free fatty acids is to determine the acid number (or acid value) of the soap stock. The acid number is the mass of potassium hydroxide (KOH) in milligrams that is required to neutralize one gram of the chemical substance being assessed. The precise acid number as measured can vary because of the heterogeneity of the soap stock. However, as an example, a high value feed stock such as virgin soybean oil can have an acid number of about 0.35 whereas a lower value feed stock can have an acid number of about 5. Yellow grease, a low value feed stock, can have an acid number of about 15 while acidulated soap stock, also a low value feed stock, can have an acid number of about 88.

Systems and methods herein can advantageously use low value soap stocks in order to produce biodiesel fuel while achieving high percent conversion rates. In some embodiments, the soap stock used has an acid number of about 3 (mg KOH/g oil) or greater. In some embodiments, the soap stock used has an acid number of about 5 (mg KOH/g oil) or greater. In some embodiments, the soap stock used has an acid number of about 10 (mg KOH/g oil) or greater. In some embodiments, the soap stock used has an acid number of about 50 (mg KOH/g oil) or greater. In some embodiments, the soap stock can be converted from one having an acid number of greater than or equal to 3 (mg KOH/g oil) to an acid number of less than or equal to 0.5 (mg KOH/g oil). In some embodiments, the soap stock can be converted from one having an acid number of greater than or equal to 3 (mg KOH/g oil) to an acid number of essentially 0 (mg KOH/g oil).

Alcohols

Alcohols suitable for use with the embodiments herein can include many different types of alcohols. By way of example, the alcohols can include those having from one to six carbon atoms. For example, in some embodiments, methanol is used. Methanol can be advantageous as the resulting alkyl esters (methyl esters) have a lower viscosity than higher alkyl esters. However, in some embodiments ethanol is used. Ethanol has low toxicity and is readily produced from plant matter by fermentation processes. In some embodiments, the alcohols suitable for use herein are around 95% to 97% pure, with the balance being made up of water. Without wishing to be bound by theory, it is believed that adding CO₂ to the alcohol feed stock or to the reaction mixture can result in the formation of carbonic acid within the water fraction of the alcohol feedstock or the reaction mixture. It is further believed that having carbonic acid and/or one or more acids present in the reaction mixture can increase the rate of esterification and/or transesterification and drive the reaction to completion such that the acid number is less than 0.5. In some embodiments, the reaction can be driven to completion such that the acid number is close to zero.

In some embodiments, the alcohols suitable for use herein can include water present in an amount equal to at least 0.05 wt. %, 0.1 wt. %, 1.0 wt. %, 2 wt. %, 3 wt. %, 4 wt. %, 5 wt. %, 6 wt. %, 7 wt. %, 8 wt. %, 9 wt. %, 10 wt. %, 15 wt. %, 20 wt. %, 25 wt. %, 30 wt. %, 40 wt. %, or 50 wt. % of the mass of the alcohol added. It will be appreciated that amount of water present in the alcohols suitable for use herein can be within a range, wherein any of the forgoing weight percentages can serve as the lower or upper bound of the range, provided that the lower bound of the range is a value less than the upper bound of the range.

In some embodiments, a single alcohol is used. In other embodiments, a mixture of different alcohols is used. By way of example, a mixture of methanol and a higher molecular weight alcohol can be used. Such a mixture can offer the advantage of being more miscible with the acidified soap stock than methanol alone.

Acids

Acids suitable for use with the embodiments herein can include many different types of acids. Without being bound by theory, it is believed that addition of acid can further catalyze the esterification of free fatty acids present in feed stocks or those that arise from the lipolysis of triglycerides during processing. By way of example, the acids can include one or more of an organic acid, an inorganic acid, a Bronsted acid, or a Lewis acid. Suitable organic acids for use herein can include, but not be limited to formic, acetic, propionic, butyric, valeric, caproic, oxalic, lactic, malic, citric, benzoic, carbonic, phenol, and uric acids, and the like. Suitable inorganic acids for use herein can include, but not be limited to, hydrochloric, nitric, phosphoric, sulfuric, boric, chloric, hydrofluoric, hydrobromic, perchloric, and hydroiodic acids. It will be appreciated that suitable Bronsted acids can include any of the forgoing organic acids or inorganic acids. Additional Bronsted acids can be include pyrophosphoric acid, methanethiol, chromic acid, permanganic acid, phytic acid and ethylenediamine tetramethyl phosphonic acid (EDTPA). Suitable Lewis acids can include, but not be limited to trimethylamine, tetrhydrofuran, diethylether, acetonitrile, quinuclidine, pyridine, acetone, ethylacetate, dimethylsulfoxide, dimethylacetamide, tetryhydrothiophene, trimethylphosphine, and the like.

Catalysts

Catalysts herein can include those exhibiting sufficient stability in the presence of supercritical conditions for the alcohols and acids described herein. For example, the supercritical conditions for methanol include T≥240° Celsius and P≥1150 psi and the supercritical conditions for ethanol include T≥240° Celsius and P≥890 psi. In some embodiments, the catalysts herein can include those exhibiting sufficient stability in the presence of supercritical temperatures and pressures for water (i.e., T≥350° Celsius and P≥3200 psi).

Catalysts herein can include metals, metal oxides, ceramics, and the like. Catalysts used with embodiments herein can include metal oxides with surfaces including Lewis acid sites, Bronsted base sites, and Bronsted acid sites. By definition, a Lewis acid is an electron pair acceptor. A Bronsted base is a proton acceptor and a Bronsted acid is a proton donor. In some embodiments, the metal oxide catalyst has been pretreated with a Bronsted acid or a Bronsted base. In some embodiments, the metal oxide catalyst can be treated with a Bronsted, including but not limited to, hydrobromic acid, hydrochloric acid, hydroiodic acid, nitric acid, sulfuric acid, perchloric acid, boric acid, chloric acid, phosphoric acid, pyrophosphoric acid, methanethiol, chromic acid, permanganic acid, phytic acid and ethylenediamine tetramethyl phosphonic acid (EDTPA).

Catalysts of embodiments herein can specifically include unmodified metal oxides including zirconia, titania, hafnia, yttria, tungsten (VI) oxide, manganese oxide, nickel oxide, nickel, copper oxide, niobium oxide, cobalt oxide, carbon, carbon/nickel, carbon/platinum. In some embodiments catalysts can include alumina, iron oxide, metal salts, insoluble metal salts, metal oxides, metal hydroxides, metal alloys, metal complexes, and metal ion complexes. Metals of these can include alkali metals, alkaline earth metals, transition metals and poor metals. In some embodiments, the metal can include one or more of group IA, IIA, IIB, IVB, VB, VIB, VIIB, VIIIB, IB, IIB, IIIA, IVA metals. In some embodiments, the catalyst can include one or more of CuO, KH₂PO₄, Nb₂O₅, Y₂O₃, ZnO, MgCO₃, K₂CO₃, Fe₂O₃, and CoO₂. In some embodiments, the catalyst can consist essentially of one or more of any of the materials described herein.

In some embodiments, the catalyst can be, or include, a metal oxide that is stable at temperatures above 250° Celsius in the presence of supercritical alcohol. In some embodiments, the catalyst can be, or include, a metal oxide that is stable at temperatures above 350° Celsius in the presence of supercritical alcohol. In some embodiments, the catalyst can be, or include, a metal oxide that is stable at temperatures above 400° Celsius in the presence of supercritical alcohol. In some embodiments, the catalyst can be, or include, a metal oxide that is stable at temperatures above 450° Celsius in the presence of supercritical alcohol. In some embodiments, the catalyst can be, or include, a metal oxide that is stable at temperatures above 500° Celsius in the presence of supercritical water. In some embodiments, the catalyst can consist essentially of any of the foregoing.

In some embodiments, the catalyst can be, or include, a metal oxide that is stable at temperatures above 350° Celsius in the presence of supercritical water. In some embodiments, the catalyst can be, or include, a metal oxide that is stable at temperatures above 400° Celsius in the presence of supercritical water. In some embodiments, the catalyst can be, or include, a metal oxide that is stable at temperatures above 450° Celsius in the presence of supercritical water. In some embodiments, the catalyst can be, or include, a metal oxide that is stable at temperatures above 500° Celsius in the presence of supercritical water. In some embodiments, the catalyst can be, or include, a metal oxide that is stable at temperatures above 550° Celsius in the presence of supercritical water. In some embodiments, the catalyst can consist essentially of any of the foregoing.

Catalysts of embodiments herein can also include silica clad with any of the foregoing catalyst materials, such as a metal oxide selected from the group consisting of zirconia, titania, hafnia, yttria, tungsten (VI) oxide, manganese oxide, nickel oxide, nickel, copper oxide, niobium oxide, cobalt oxide, carbon carbon/nickel, carbon/platinum.

In some embodiments, the catalyst can be of a single metal oxide type. By way of example, in some embodiments, the catalyst is substantially pure zirconia. By way of example, in some embodiments, the catalyst is substantially pure titania. By way of example, in some embodiments, the catalyst is substantially pure hafnia. By way of example, in some embodiments, the catalyst is substantially pure yttria. By way of example, in some embodiments, the catalyst is substantially pure tungsten (VI) oxide. By way of example, in some embodiments, the catalyst is substantially pure manganese oxide. By way of example, in some embodiments, the catalyst is substantially pure nickel oxide.

Catalysts of embodiments herein can also include mixtures of materials, such as mixtures of materials including zirconia, titania, hafnia, yttria, tungsten (VI) oxide, manganese oxide, nickel oxide, nickel, carbon, carbon/nickel, and carbon/platinum.

In some embodiments, the catalyst can consist essentially of zirconia. Zirconia catalyst particles for use herein can be thermally and chemically stable under supercritical alcohol conditions (e.g., T≥240° Celsius and P≥850 psi). Zirconia catalyst particles for use herein can also be thermally and chemically stable under supercritical water conditions (i.e., T≥350° Celsius and P≥3,200 psi). Exemplary zirconia catalysts are commercially available from ZirChrom Separations of Anoka, Minn. Suitable zirconia catalyst particles for use herein can maintain a well-defined pore structure and are stable under both high pressure (6,000 psi) and high temperature (600° Celsius) conditions. In some embodiments, the zirconia catalyst can be porous and spherical, with an average diameter of 25 microns. Zirconia is also well-suited for the embodiments herein due to its high chemical stability over the entire pH range, from pH of 1 to a pH of 14.

Metal oxide catalysts of embodiments herein can include metal oxide particles clad with carbon. Carbon clad metal oxide particles can be made using various techniques such as the procedures described in U.S. Pat. Nos. 5,108,597; 5,254,262; 5,346,619; 5,271,833; and 5,182,016, the contents of which are herein incorporated by reference. Carbon cladding on metal oxide particles can render the surface of the particles more hydrophobic.

Metal oxide catalysts suitable for use herein can also include polymer coated metal oxides. By way of example, metal oxides herein can include a metal oxide coated with polybutadiene (PBD). Polymer coated metal oxide particles can be made using various techniques such as the procedure described in Example 1 of U.S. Pub. No. 2005/0118409, the content of which is herein incorporated by reference. Polymer coatings on metal oxide particles can render the surface of the particles more hydrophobic.

Metal oxide catalysts of embodiments herein can be made in various ways. As one example, a colloidal dispersion of zirconium dioxide can be spray dried to produce aggregated zirconium dioxide particles. Colloidal dispersions of zirconium dioxide are commercially available from Nyacol Nano Technologies, Inc., Ashland, Mass. The average diameter of particles produced using a spray drying technique can be varied by changing the spray drying conditions. Examples of spray drying techniques are described in U.S. Pat. Nos. 4,138,336 and 5,108,597, the contents of both of which are herein incorporated by reference. It will be appreciated that other methods can also be used to create metal oxide particles. One example is an oil emulsion technique as described in Robichaud et al., Technical Note, “An Improved Oil Emulsion Synthesis Method for Large, Porous Zirconia Particles for Packed- or Fluidized-Bed Protein Chromatography,” Sep. Sci. Technol. 32, 2547-59 (1997). A second example is the formation of metal oxide particles by polymer induced colloidal aggregation as described in M. J. Annen, R. Kizhappali, P. W. Carr, and A. McCormick, “Development of Porous Zirconia Spheres by Polymerization-Induced Colloid Aggregation-Effect of Polymerization Rate,” J. Mater. Sci. 29, 6123-30 (1994). A polymer induced colloidal aggregation technique is also described in U.S. Pat. No. 5,540,834, the contents of which are herein incorporated by reference.

Metal oxide catalysts suitable for use with the embodiments herein can be sintered by heating them in a furnace or other heating device at a relatively high temperature. In some embodiments, the metal oxide is sintered at a temperature of about 160° C. or greater. In some embodiments, the metal oxide is sintered at a temperature of about 400° C. or greater. In some embodiments, the metal oxide is sintered at a temperature of about 600° C. or greater. Sintering can be done for various amounts of time depending on the desired effect. Sintering can make metal oxide catalysts more durable. In some embodiments, the metal oxide is sintered for more than about 30 minutes. In some embodiments, the metal oxide is sintered for more than about 3 hours. However, sintering also reduces the surface area. In some embodiments, the metal oxide is sintered for less than about 1 week.

In some embodiments, the catalyst is in the form of particles. Particles within a desired size range can be specifically selected for use as a catalyst. For example, particles can be sorted by size using techniques such as air classification, elutriation, settling fractionation, or mechanical screening. In some embodiments, the size of the particles is greater than about 0.2 μm. In some embodiments, the size range selected is from about 50 nm to about 50 mm. In some embodiments, the size range selected is from about 0.2 μm to about 10 mm. In some embodiments, the size range selected is from about 0.2 μm to about 5 mm. In some embodiments, the size range selected is from about 0.2 μm to about 2 mm. In some embodiments, the size range selected is from about 0.2 μm to about 1 mm. In some embodiments, the size range selected is from about 1 μm to about 100 μm. In some embodiments, the size range selected is from about 5 μm to about 15 μm. In some embodiments, the average size selected is about 10 μm. In some embodiments the size of the particles is about 80 μm. In some embodiments the size of the particles is about 25-35 μm. In some embodiments, the average size selected is about 5 μm.

In some embodiments, the catalyst can be a particulate in the nanometer size range. In some embodiments, the catalyst can be from about 0.1 nm to about 500 nm. In some embodiments, the catalyst can be from about 1.0 nm to about 300 nm. In some embodiments, the catalyst can be from about 5.0 nm to about 200 nm. In some embodiments, the catalyst can be used in the form of a colloid.

In some embodiments, catalyst particles used with embodiments herein can be porous. By way of example, in some embodiments the particles can have an average pore size of about 30 angstroms to about 2000 angstroms. However, in other embodiments, catalyst particles used are non-porous.

The physical properties of a porous catalyst can be quantitatively described in various ways such as by surface area, pore volume, porosity, and pore diameter. In some embodiments, catalysts of embodiments herein can have a surface area of between about 1 and about 1000 m²/gram. In some embodiments, catalysts of embodiments herein can have a surface area of between about 1 and about 400 m²/gram. In some embodiments, the catalyst of embodiments herein can have a surface area much higher than 400 m²/gram.

In some embodiments, catalysts of embodiments herein can have a surface area of between about 1 and about 200 m²/gram. Pore volume refers to the proportion of the total volume taken up by pores in a material per weight amount of the material. In some embodiments, catalysts of embodiments herein can have a pore volume of between about 0.01 ml/g and about 2 ml/g. In some embodiments, catalysts of embodiments herein can have a pore volume of between about 0 ml/gram and 0.6 ml/gram. Porosity refers to the proportion within a total volume that is taken up by pores. As such, if the total volume of a particle is 1 cm³ and it has a porosity of 0.5, then the volume taken up by pores within the total volume is 0.5 cm³. In some embodiments, catalysts of embodiments herein can have a porosity of between about 0 and about 0.8. In some embodiments, catalysts of embodiments herein can have a porosity of between about 0.3 and 0.6.

Catalyst particles suitable for use with the embodiments herein can have various shapes. By way of example, in some embodiments the particle can be in the form of spherules. In other embodiments, the particle can be a monolith. In some embodiments, the particle can have an irregular shape.

Metal oxides suitable for use with the embodiments herein can include metal oxides whose surfaces are dominated by Lewis acid-base chemistry. A Lewis acid is an electron pair acceptor. Metal oxides herein can have Lewis acid sites on their surface and can specifically include alumina, zirconia, titania and hafnia. Metal oxides herein can also include silica clad with a metal oxide selected from the group consisting of zirconia, alumina, titania, hafnia, zinc oxide, copper oxide, magnesium oxide and iron oxide. In some embodiments, metal oxides can include yttria (yttrium oxide), such as ytrria stabilized zirconia. In some embodiments, metal oxides can include magnesium oxide and/or cerium dioxide. Metal oxides herein can also include mixtures of metal oxides. Specifically metal oxides herein can include mixtures including one or more of zirconia, alumina, titania and hafnia.

One issue associated with many previous methods for producing biodiesel is that the catalysts used are subject to poisoning over time. Specifically, many existing catalysts are affected by the reaction conditions (e.g., pH, temperature, pressure) in a manner so as to reduce reaction yield over time. However, some embodiments of metal oxide catalysts as described herein are advantageous because they are highly resistant to poisoning over time. This is particularly significant in the context of supercritical reaction conditions, which may otherwise tend to promote catalyst poisoning. Of the various metal oxides that can be used with embodiments herein, zirconia, titania and hafnia offer particular advantages because they are very chemically and thermally stable and can withstand very high temperatures and pressures (such as supercritical conditions for various alcohols) as well as extremes in pH. Such catalysts can exhibit a resistance to poisoning over time. In some embodiments, the metal oxide catalyst can include zirconia, titania, and/or hafnia. Zirconia and hafnia are even more thermally stable than titania. In some embodiments, the metal oxide catalyst can include zirconia and/or hafnia.

Some feed stocks may include components, such as lecithin, that can lead to the deposit of residues resulting in clogging and/or obstruction of a transesterification reactor. The significant thermal stability of metal oxides suitable for use with the embodiments herein can be advantageous in this context because the reactor can be cleaned out through the use of an oxygen containing gas or liquid at extremely high temperatures to combust any residue that has been deposited on the metal oxide catalyst, thereby cleaning the reactor and returning it to its original state. Other types of catalysts may not have sufficient thermal stability to perform such a cleaning/regeneration process.

In some embodiments, the metal oxides used suitable for use with the embodiments herein can be bare or unmodified. As used herein, the term “unmodified metal oxide” shall refer to a metal oxide that includes substantially only the metal oxide at its surface, and thus does not include significant concentrations of chemical groups such as phosphates or sulfates on its surface. Many conventional catalyst materials include various modifying groups to enhance catalysis. However, as shown in the examples herein, unmodified metal oxides can surprisingly be used to achieve high conversion percentages and relatively small residence times.

However, in other embodiments, metal oxides suitable for use with the embodiments herein can be modified with another compound. For example, the Lewis acid sites on metal oxides herein can interact with Lewis basic compounds. Thus, metal oxides herein can be modified by adsorbing Lewis basic compounds to the surface of metal oxides ntion. A Lewis base is an electron pair donor. Lewis basic compounds herein can include anions formed from the dissociation of acids such as hydrobromic acid, hydrochloric acid, hydroiodic acid, nitric acid, sulfuric acid, perchloric acid, boric acid, chloric acid, phosphoric acid, pyrophosphoric acid, methanethiol, chromic acid, permanganic acid, phytic acid and ethylenediamine tetramethyl phosphonic acid (EDTPA).

While not intending to be bound by theory, the use of strong acids as a modifying agent for the metal oxide catalysts herein can be advantageous because they absorb more strongly to the Lewis acid sites on the metal oxide and thus be less likely to leach off into the reaction mixture. Exemplary acids include phosphoric acid.

Lewis basic compounds to be used as a modifying agent for the metal oxide catalysts herein can include hydroxide ion as formed from the dissociation of bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and the like.

The Lewis acid sites on catalysts of embodiments herein can interact with Lewis basic compounds. Thus, in some embodiments, Lewis basic compounds can be bonded to the surface of catalysts. However, in other embodiments, the catalysts used with embodiments herein are unmodified and have no Lewis basic compounds bonded thereto. A Lewis base is an electron pair donor. Lewis basic compounds of embodiments herein can include anions formed from the dissociation of acids such as hydrobromic acid, hydrochloric acid, hydroiodic acid, nitric acid, sulfuric acid, perchloric acid, boric acid, chloric acid, phosphoric acid, pyrophosphoric acid, chromic acid, permanganic acid, phytic acid and ethylenediamine tetramethyl phosphonic acid (EDTPA), and the like. Lewis basic compounds of embodiments herein can also include hydroxide ion as formed from the dissociation of bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and the like.

The anion of an acid can be bonded to a metal oxide of embodiments herein by refluxing the metal oxide in an acid solution. By way of example, metal oxide particles can be refluxed in a solution of sulfuric acid. Alternatively, the anion formed from dissociation of a base, such as the hydroxide ion formed from dissociation of sodium hydroxide, can be bonded to a metal oxide by refluxing in a base solution. By way of example, metal oxide particles can be refluxed in a solution of sodium hydroxide. The base or acid modification can be achieved under exposure to the acid or base in either batch or continuous flow conditions when disposed in a reactor housing at elevated temperature and pressure to speed up the adsorption/modification process. In some embodiments, fluoride ion, such as formed by the dissociation of sodium fluoride, can be bonded to the particles.

In some embodiments, catalyst particles can be packed into a housing, such as a column. In some embodiments, the column is a reactor. The metal oxide particles disposed in a housing can form a fixed-bed reactor. Disposing catalyst particles in a housing is one approach to facilitating continuous flow processes. Many different techniques can be used for packing the catalyst particles into a housing. The specific technique used may depend on factors such as the average particle size, the type of housing used, etc. Generally speaking, particles with an average size of about 1-20 microns can be packed under pressure and particles with an average size larger than 20 microns can be packed by dry-packing/tapping methods or by low pressure slurry packing. In some embodiments, the catalyst particles of embodiments herein can be impregnated into a membrane, such as a PTFE membrane.

However, in some embodiments, catalysts suitable for use with the embodiments herein are not in particulate form. For example, a layer of a metal oxide can be disposed on a substrate in order to form a catalyst. The substrate can be a surface that is configured to contact the feedstocks during processing. In one approach, a catalyst can be disposed as a layer over a surface of a reactor that contacts the feedstocks. Alternatively, the catalyst can be embedded as a particulate in the surface of an element that is configured to contact the feedstocks during processing.

Example 1: Formation of Alkyl Esters

A fixed-bed reactor reaction vessel is packed with a particulate titania catalyst. An acidified soap stock is mixed with methanol. Carbon dioxide is added to the mixture. The mixture is pumped under pressure into the fixed-bed reactor reaction vessel. The pressure and temperature in the reaction vessel are supercritical for methanol. The pressure in the reaction vessel is greater than 1154 PSI and the temperature is greater than 240 degrees Celsius. A reaction product mixture is obtained. The reaction product mixture includes alkyl esters.

Example 2: Formation of Alkyl Esters

A fixed-bed reactor reaction vessel is packed with a particulate zirconia catalyst. An acidified soap stock is mixed with ethanol. Carbon dioxide is added to the mixture. The mixture is pumped under pressure into a fixed-bed reactor reaction vessel. The pressure and temperature in the reaction vessel are supercritical for ethanol. The pressure in the reaction vessel is greater than 915 PSI and the temperature is greater than 240.9 degrees Celsius. A reaction product mixture is obtained. The reaction product mixture includes alkyl esters.

It should be noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the content clearly dictates otherwise. Thus, for example, reference to a composition containing “a compound” includes a mixture of two or more compounds. It should also be noted that the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise.

It should also be noted that, as used in this specification and the appended claims, the phrase “configured” describes a system, apparatus, or other structure that is constructed or configured to perform a particular task or adopt a particular configuration to. The phrase “configured” can be used interchangeably with other similar phrases such as arranged and configured, constructed and arranged, constructed, manufactured and arranged, and the like.

All publications and patent applications in this specification are indicative of the level of ordinary skill in the art to which this invention pertains. All publications and patent applications are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated by reference.

The embodiments described herein are not intended to be exhaustive or to limit the invention to the precise forms disclosed in the following detailed description. Rather, the embodiments are chosen and described so that others skilled in the art can appreciate and understand the principles and practices. As such, aspects have been described with reference to various specific and preferred embodiments and techniques. However, it should be understood that many variations and modifications may be made while remaining within the spirit and scope herein. 

1. A process for producing alkyl esters comprising: mixing an acidified soap stock with an alcohol, water, carbon dioxide and/or one or more acids to form a reaction mixture; and contacting the reaction mixture with a catalyst under supercritical conditions for the alcohol, the catalyst comprising a metal oxide.
 2. The process of claim 1, the metal oxide selected from the group consisting of alumina, titania, zirconia, and hafnia. 3-4. (canceled)
 5. The process of claim 1, the soap stock comprising a byproduct derived from tall oil, rapeseed oil, soybean oil, canola oil, cottonseed oil, grape seed oil, mustard seed oil, corn oil, linseed oil, sunflower oil, poppy-seed oil, walnut oil, peanut oil, rice bran oil, camellia oil, castor oil, and olive oil, palm kernel oil, coconut oil, rice oil, algae oil, seaweed oil, or Chinese Tallow tree oil.
 6. The process of claim 1, the soap stock having an acid number of greater than or equal to 3 mg KOH/g oil.
 7. The process of claim 6, wherein the step of contacting the reaction mixture with a catalyst comprises conversion of the soap stock from an acid number of equal to 3 mg KOH/g oil to an acid number of less than or equal to 0.5 mg KOH/g oil.
 8. The process of claim 1, the acid comprising an organic acid.
 9. The process of claim 1, the acid comprising a Bronsted acid.
 10. The process of claim 1, the acid comprising an inorganic acid.
 11. The process of claim 1, further including mixing an inorganic base or and organic base into the reaction mixture.
 12. The process of claim 1, wherein the step of contacting the reaction mixture with a catalyst is performed at a temperature of between 200 and 400 degrees Celsius.
 13. The process of claim 1, wherein the step of contacting the reaction mixture with a catalyst is performed at a pressure of between 1000 and 5000 psi. 14-18. (canceled)
 19. The process of claim 1, the alcohol comprising a C1-C6 alcohol.
 20. The process of claim 1, the alcohol comprising an alcohol selected from the group consisting of methanol and ethanol. 21-24. (canceled)
 25. The process of claim 1, wherein carbon dioxide is present in an amount equal to at least 0.1 wt. percent of the mass of the alcohol added.
 26. The process of claim 1, wherein carbon dioxide is present in an amount equal to at least 0.5 wt. percent of the mass of the alcohol added.
 27. The process of claim 1, the reaction mixture comprising carbonic acid.
 28. The process of claim 1, the reaction mixture comprising carbonic acid at concentration of at least 0.05 M.
 29. The process of claim 1, the reaction mixture comprising carbonic acid at concentration of at least 1 M.
 30. The process of claim 1, wherein the pH of the reaction mixture is less than
 7. 31. The process of claim 1, wherein the pH of the reaction mixture is less than
 3. 32-36. (canceled) 